Fuel compositions



atent @hfice 3,024,095 Patented Mar. 6, 1 062 3,024,096 FUEL COMPOSITEGNS John D. Zeeh, Wilmington, Del., assignor to Atlas Chemical Industries, Inc, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Aug. 29, 1958, Ser. No. 757,906 Claims. (Cl. 44-63) This invention relates to liquid hydrocarbon fuel compositions to which anti-static properties have been imparted and to methods of producing the same. Particularly it relates to liquid hydrocarbon fuels which have had their electrical characteristics changed by the addition of anti-static agents which are condensation products of mono and poly (hydroxyhaloalkyl) ethers of polyhydric alcohols and acylated polyamines.

Modern engines of the internal combustion type, such as are used in automotive vehicles and propeller driven aircraft, and jet engines, such as are used in military aircraft, make use of a wide variety of liquid hydrocarbon fuels. serious safety hazard because of their property of forming an explosive equilibrium mixture with air at temperatures encountered under normal storage and handling conditions. Handling these fuels has, in the past, presented a considerable danger because such explosive mixtures may be readily ignited by discharges of static electricity which has been accumulated in the fuel in the course of pumping and transfer operations.

Not all fuels have volatility characteristics which ordinarily permit formation of explosive equilibrium mixtures at normal temperatures. Some fuels have such high volatility that they may not be expected to form such an explosive equilibrium mixture, except at temperatures below those normally encountered, because the vapor mixtures they form in equilibrium with air are too rich to be exploded. On the other hand, other fuels have such low volatility that, except under temperature conditions higher than those normally encountered, they may ordinarily not be expected to produce vapor mixtureswhich are rich enough to explode.

It should be appreciated that the above discussion is confined to equilibrium conditions. Fuels which do not normally form equilibrium explosive mixtures with air at normal temperatures may form explosive mixtures when compressed or when present with air in the form of a foam or froth. Thus, although automotive fuels do not form explosive equilibrium mixtures above 10 F., it is possible to obtain such mixtures in refinery operations at higher temperatures. For instance, when a tankful of automotive gasoline is blended by rolling with air (i.e. air is sparged into the tank as a source of agitation) an explosive mixture can be artificially created.

In general, the fuels with which the present invention will find its principal applicability are those having such volatility characteristics that, within a temperature range between about -20 F. and about 210 F., explosive equilibrium mixtures form in air and more particularly those which form such mixtures between about -20 F. and about 100 F.

Reid vapor pressure, which is measured at 100 F., is one common measure of volatility characteristics. Fuels suitable for use in this invention will be found included within the range of Reid vapor pressures of from about 0.1 to about pounds per square inch.

One of the fuels with which the invention is particularly applicable is JP4 jet fuel, which is completely described in military specification MIL F5624 C. JP-4 fuel which is a low vapor pressure, wide-cut, gasoline type hydrocarbon, forms an equilibrium explosive mixture with air between about 10 F. and about 90 F. and.

has a Reid vapor pressure of from 2 to 3 pounds. An-

Many of these fuels have been found to present a other fuel with which the invention may be employed is JP-3 jet fuel, which forms such mixtures at about 45 F. and below, and has a Reid vapor pressure between 5 and 7 pounds per square inch. The invention is also applicable to fuels which are used in internal combustion engines, as, for example, high test aviation gasoline which forms explosive mixtures at about 30 F. and below, and has a Reid vapor pressure between 5.5 and 7 pounds per square inch. It is also useful with kerosene and with ordinary automotive gasoline, which latter forms such explosive equilibrium mixtures of about 10 F. and below and has a Reid vapor pressure between 10 and 15 pounds per square inch. All of these fuels may be successfully treated in the manner described below and, when so treated, are within the scope of this invention.

When dealing with fuels, such as those discussed above, it has been found that an explosion can be triggered by the spark from a charge of static electricity such as can be built up in the fuel body in the course of pumping and filling operations. WADC Technical Report 55-266 of November 1954, entitled Frictional Electrification Effects in Fuel Flow by Dr. F. M. Ernsberger of the Southwest Research Institute (catalogued by ASTIA as AD No. 90288) is a detailed study of the theoretical aspects of this problem. In order to minimize such dangers, many precautions are now taken such as elaborate grounding systems and the use of oversize pipe lines to minimize friction and consequent static build-up.

It has been empirically determined that there is a relationship between the electrical resistivity of liquid hydrocarbon fuels and their ability to build up a charge of static electricity such as is necessary to trigger an explosion. Fuels which have an electrical resistivity of less than about 1 10 ohnrcentimeters cannot build up such a charge since the static charge created in such fuels is able, by virtue of the low resistivity thereof, to ground itself as fast as it builds up.

An object of this invention is accordingly, the provision of liquid hydrocarbon fuel in which static electricity build up during storage or handling is inhibited so as to minimize the possibility of accidental ignition.

An addtional object of this invention is the provision of a fuel composition which is rendered highly conductive by the use of small amounts of selected additives, which additives do not interfere with the combustion characteristics of said fuel.

The above objects of this invention, as well as additional objects, will be apparent to those skilled in the art from a consideration of the following description and examples.

Briefly stated, it has been found that the fuels of the present invention have, lower electrical resistivity (i.e. greater conductivity) and are inhibited against the buildup of static electricity by the addition of a small amount of anti-static agents which are compounds prepared by a process which comprises reacting a fatty acid-polyamine derivative, which contains basic nitrogen, with a hydroxy haloalkyl ether of a polyhydric alcohol, said alcohol containing at least three hydroxyl groups per molecule, said reactants having been selected in such proportions that from one to two basic nitrogen atoms are present in the molecule of polyamine derivative for each halogen atom in said hydro-xy haloalkyl ether.

The amount of additives of the invention desirable for anti-static protection is that which is sufficient to reduce the electrical resistivity of the fuel to a value below about 1 1O ohm-centimeters. Usually an amount less than 2 wt. percent will suffice and amounts between 005% and 1.0% by weight are preferred.

The synthesis of the additives employed in this invention involves the following steps:

(1) A polyhydric alcohol containing three or more hydroxyl groups per molecule, preferably a hexitol, is condensed with a reactive epihalohydrin such as, for example, epichlorohydrin.

(2) Separately, a polyalkylene polyamine is reacted with a fatty acid (or its equivalent) and also, if desired, with a short chain aliphatic acid (or its equivalent) under conditions producing carbon to nitrogen bonding. The reactants must be selected in such proportions that the resulting polyamine derivative contains residual basic nitrogen.

(3) The product of step (1) is brought into reaction with the product of step (2) in such proportions that from one to two basic nitrogen equivalents are present for each halogen equivalent, thus forming a cationic surfaceactive salt which is a hydrohalide or a quaternary halide. These compounds have anti-static properties and are preferred for use in the invention.

(4) If desired, the surface-active free base may be liberated by treating the salt with an alkali. The free bases are also suitable for anti-static use in accordance with the invention. Thereafter, the free base may be reacted with various organic and inorganic acids includ- 9 ing mineral acids such as, for example, phosphoric and sulfuric acid, to form other acid salts which also have surface-active properties. These compounds also have anti-static properties, and may be formulated with hydrocarbon fuels to reduce the resistivity thereof.

The initial step of the synthesis is exemplified by the condensation of a polyhydric alcohol having three or more hydroxyl groups per molecule with epichlorohydrin in the presence of a catalyst. The reaction can be represented by the following chemical equation:

mom. nontonorncl R In the above equation x is a number of three or more and n is a number from one to x. R is an hydroxyl-free radical of a polyhydric alcohol. When the polyhydric alcohol is a hexitol, from one to about three mols of epichlorohydrin are usually preferred.

The reaction illustrated above may be performed in the presence of an acidic catalyst as is well known in the prior art. Preferred catalysts are those of the Lewis acid type which include, for example, BF BF etherate, AlCl and SnCL; but H 50 p-tolucne sulfonic acid and the like may also be used.

The reaction may be carried out over a wide range of temperature conditions. Below about 50 C. reaction times with higher polyhydric alcohols tend to become unduly long although reactions involving glycerin can be readily performed at that temperature. Above about 130 C. some polyhydric alcohols, for example hexitols, tend to undergo undesirable decomposition and color formation, but with less sensitive polyhydric alcohols temperatures as high as 175 C. may be used. A preferred temperature range is that between 90 and 130 C.

The reaction may be performed at any convenient pressure. While atmospheric pressure is most convenient, the exact reaction conditions chosen are a function of the reactants used and the desired speed of reaction. Thus, when the reactants are sorbitol (which solidifies at about 90-95 C.) and epichlorohydrin (which boils at about 117 C.), it is preferred to carry the reaction out at about 100110 C. and atmospheric pressure.

While the reaction is generally carried out in the absence of solvent or diluent, such materials may be used if desired to lower the viscosity, as an aid in controlling temperature, or to permit the use of lower temperatures where high melting polyhydric alcohols (such as hexitols) are used.

Suitable polyhydric alcohols or mixtures thereof for use in this connection include, among others, triols (such as glycerol), tetriotols (such as erythritol), pentitols (such as xylitol, arabitol, etc.), the hexitols (such as sorbitol, mannitol, dulcitol, etc.), polyhydric alcohols containing more than six hydroxy groups and polyhydric alcohols such as pentaerythritol, trimethylolethane, trimethylolpropane and other polymethylol alkanes.

Suitable polyhydric alcohols also include anhydro derivatives of other polyhydric alcohols (having at least three hydroxy groups per molecule) in which water has been removed from two hydroxyl groups to form a cyclic ether, such as 1,4 sorbitan, and also external ethers of polyhydric alcohols, as, for example, diglycerol.

Another group of suitable polyhydric alcohols comprises the monosaccharides such as sorbose, mannose, glucose, arabinose and xylose as well as methyl glucoside and similar compounds.

The polyhydric alcohols useful in this invention include those, of the type listed above, which have been modified by etherification with alkylene oxides such as ethylene oxide, 1,2 propylene oxide and mixtures thereof. As is well known in the art, such a reaction yields products containing polyoxyalkylene chains of varying length. If a mixture of alkylene oxides is employed, a given poly oxyalkylene chain may contain both the oxyethylene group and the oxypropylene groups. For the purpose of utilization in this invention the most suitable polyoxyalkylene ethers of polyhydric alcohols are those formed by reacting from one to six mols of alkylene oxide with each mol of polyhydric alcohol. The term polyhydric alcohol when used hereafter is intended to include all of the above exemplified compounds and mixtures thereof.

In lieu of epichlorohydrin other reactive epihalohydrins may be used such as epibromohydrin and epiiodohydrin. Other compounds such as 1-chloro-2,3 epoxybutane and 2-chloro-3,4 epoxybutane are also suitable for producing mono and polyhydroxy haloalkyl ethers of polyhydric alcohols. However, fluorine is not usually preferred for use in this connection, and consequently the halogen employed should preferably be one having an atomic weight above 30.

The condensation products of this reaction are, for the most part, very viscous syrups. They are complex mixtures which may contain residual free polyhydric alcohol in addition to various isomeric epihalohydrinpolyhydric alcohol condensates (i.c. chlorhydroxypropyl ethers).

The second synthesis step is the carbon to nitrogen bond-forming reaction of a fatty acid (or its equivalent) with a polyalkylene polyamine.

The chemistry of the amidation reaction between polyalkylene polyamines and fatty acid has been well elucidated in the prior art. Under comparatively mild reaction conditions, a carbon to nitrogen bond is created and simple amides of the polyamines consequently are formed. Depending on the proportion of reactants the amides which are formed may be mono-amides, diamides or higher amides. Under more severe conditions. particularly at high temperatures, some of the first formed amides undergo a ring closing dehydration to form substituted cyclic nitrogen compounds as, for example, substituted imidazolines, and substituted tetrahydropyrimidines.

To prepare the intermediates of this step, a fatty acid preferably containing from 12 to 22 carbon atoms, such as for example lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, dodecylenic, palmitoleic, oleic, ricinoleic, linoleic, linolenic, elostearic, licanic, behenic, erucic or a naphthenic acid is brought into reaction with a polyalkylene polyamine. Mixtures of these acids may also be used.

Naturally occuring fats may be used in place of fatty acids. Suitable ones include, for example, tallow, lard, cottonseed oil, soybean oil, corn oil, castor oil, coconut also suitable reactants.

ing from 3 to amino groups.

oil and mixtures thereof. Mixtures of higher'fatty acids derived from these fats, such as, for example, coconut fatty acids, lard fatty acids and cottonseed fatty acids may also be used. Aliphatic mono-carboxylic acids derived from petroleum by oxidation are also suitable.

Fatty acid esters, preferably lower alkyl esters, are When an ester is employed at the source of fatty acid, the by-product of the reaction is the corresponding alcohol instead of water. It may be removed by a distillation, if desired, or may be left in the reaction mixture as a diluent. All of the above materials are intended to be included Within the scope of the term fatty acid henceforth.

It is also possible to modify the hydrophilic character of the products of the invention by partially amidating the polyamine with at least one molecule of a long chain fatty acid of the type described above and also amidating other amino nitrogens with a short chain (2 to 6 carbon atoms per molecule) aliphatic acid or its equivalent.

The polyamines with which the above acids or acid equivalents are reacted are preferably polyethylene or polypropylene polyamines, or mixtures thereof, contain- Suitable polyamines include, among others, diethylene triamine, triethylene triamine (N-aminoethyl piperazine), triethylene tetramine, tetraethylene pentamine, hydroxyethyl diethylene triamine (and other reaction products of alkylene oxides such as ethylene and propylene oxide and polyalkylene polyamines provided however that the resulting amine contain at least one amino hydrogen), dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, compounds similar to 3,3 iminobispropylamine and mixtures of these compounds.

The proportion of reactants used must be such that the number of amine equivalents in the product exceed the equivalents of fatty acid by at least one, thus giving the product basic characteristics. Use of excess amine favors the formation of such basic compounds. For instance, Where it is desired to obtain a product having a minimum of fatty acid substitution on the polyamine, such as the mono-amide of diethylene triamine, an excess of polyamine is generally used. The excess amine can be recovered by distillation and re-cycled. to the process.

In connection with the basicity of the acylated polyamine it is important to remember that tertiary amino nitrogen atoms are incapable of amidation. Furthermore such tertiary amino nitrogen atoms exhibit basic characteristics. Therefore, even if a polyamine which contains tertiary amino nitrogen is fully amidated it still has basic properties after amidation because the tertiary amino nitrogen has not been converted to an amido nitrogen. Tertiary nitrogen atoms thus remain basic throughout the reaction and are counted as part of the excess amine equivalents in selecting the reactant proportions.

In the subsequent formation of the surfactants of this invention either the open chain amide type of derivative or the cyclized type, as exemplified by the substituted imidazolines and substituted tetrahydropyrimidines may be used. Mixtures of the two types of derivatives may also be used. In the employment of the novel compositions of the invention it usually is not of moment whether the amide or the cyclic type of configuration is present in the molecule.

When it is desired that the open chain amide structure be predominant, the reaction is carried out at relatively low temperatures, usually from about 125 to 180 C. and for short times, of about /2 to 4 hours. Higher temperatures and/ or longer times favor conversion to the imidazoline type products. Reaction temperatures up to 275 C. and times up to 1G or more hours may be utilized.

The third step in the synthesis of the hydroxyl-bearing cationic surfactants of the present invention is the reaction of the polyol-epihalohydrin ethers of step (1) with 6 the fatty acid-polyalkylene polyamine derivatives of step (2) to form salts.

The products are cationic in nature and may be characterized as salts of secondary amines, tertiary amines and quaternary ammonium bases. When the polyaminefatty acid derivative has basic characteristics due only to a tertiary amino nitrogen atom then the salts formed in this reaction will be quaternary ammonium salts. In any event all the products formed in this synthesis step contain pentavalent nitrogen. In the case of the quaternary salts, four of the valence bonds of the nitrogen are satisfied by carbon whereas in the case of the secondary and tertiary amine salts respectively, only two and three of the bonds are so satisfied.

The reactant proportions are preferably so selected that from 1 to 3, and more preferably from 1 to 2, base equivalents of the fatty acid-polyalkylene polyamine derivatives are condensed per halogen atom of the polyol-epihalohydrin ether. The reaction may be carried out at any temperature from about 75 to 150 C., the preferred range being from to C.

These salts may be converted to free bases (including quaternary hydroxides) by treatment with an alkali such as NaOl-I in a known manner.

Some of the wide variety of compounds which can be prepared in this manner may be illustrated by the following formula:

(OH)Xn wherein x is a number from 3 to 6; n is a number from 1 to x; R is a hydroxyl free radical of a polyhydric alcohol; and each A is a monovalent organic radical independently selected from the group exemplified by the following:

and substituted imidazoline and tetrahydropyrimidine derivatives of (a) such as, for example:

Hz lHz OH Wherever used in the above radicals:

a and b are integers (either of which may be zero) whose total is a whole number from 2 to .4geachrc is an integer from zero to 4 whose total value in a given radical is a number between 2 and 4; each d is an integer from zero to 2 provided that their total in a given radical does not exceed 2; e is an integer from 1 to 3; y is either 2 or 3; each B is independently selected from the group consisting of hydrogen, hydroxy lower alkyl, acyl radicals of fatty acids containing from 12 to 22 carbon atoms and acyl radicals of aliphatic acids containing from 2 to 6 carbon atoms; D is the hydrocarbon radical of an acyl variant of B; each E is independently selected from the group consisting of hydrogen and hydroxy lower alkyl; each F is independently selected from the group consisting of hydroxy lower alkyl, acyl radicals of fatty acids containing from 12 to 22 carbon atoms and acyl radicals of aliphatic acids containing from 2 to 6 carbon atoms; each G is independently selected from the group consisting of hydroxy lower alkyl and amino hydrogen; and each I is independently selected from the group consisting of acyl radicals of fatty acids containing from 12 to 22 carbon atoms and acyl radicals of aliphatic acids containing from 2 to 6 carbon atoms; provided finally that in a given radical at least one of B, D, F, or J must be long chain acyl.

After compounds of the above type have been synthesized, they may be reacted if desired with water-soluble, amine-salt-forming acids. It is thus possible to form nitrates, sulfates, alkyl sulfates and phosphates as well as organic acid salts such as formates, acetates, lactates, tartrates, benzene or toluene sulfonates and citrates.

The formation of suitable compounds is described more fully in my co-pending case, Serial No. 654,472 filed April 23, 1957 of which the instant case is a continuation-inpart. Compounds described in that case which are suitable for the purposes of this invention include those of Examples III-1 to III-17.

Anti-static additives suitable for use in this invention were synthesized in the following manner.

(A) CONDENSATION OF A POLYHYDRIC ALCOHOL WITH EPICHLOROHYDRIN Example A-1 651 grams of anhydrous sorbitol were heated to a reaction temperature of between 98 and 109 C.; 1.5 cc. of BF etherate catalyst (45% BF where then added.

Thereafter, 578 grams of epichlorohydrin (molar ratio sorbitol to epichlorohydrin of 1:1.75) were added dropwise, over a period of 45 minutes with vigorous stirring and control of cooling, so as to maintain the temperature within the specified limit. The temperature was subsequently maintained for one hour between 98 and 109 C. by the addition of heat to insure completion of the reaction.

Example A-2 913 grams of anhydrous sorbitol were heated to a reaction temperature of between 100 and 107 C.; 2.0 cc. of BB etherate catalyst (45% BF were then added. Thereafter, 1,040 grams of epichlorohydrin (molal ratio sorbitol to epichlorohydrin of 122.25) were added dropwise, over a period of one hour with vigorous stirring and control of cooling, so as to maintain the temperature within the specified limits. The temperature was subsequently maintained for an additional hour between 100 and 107 C. by the addition of heat to insure completion of the reaction.

Example A-3 1,200 grams of anhydrous sorbitol were heated to a reaction temperature of between 100 and 107 C.; 3.0 cc. of BF etherate catalyst (45% BF were then added. Thereafter, 1,220 grams of epichlorohydrin (molal ratio sorbitol to epichlorohydrin of 1:2.0) were added dropwise, over a period of 2 hours and 40 minutes with vigorous stirring and control of cooling, so as to maintain the temperature within the specified limits. The temperature was subsequently maintained for an additional hour be- 8 tween and 107 C. by the addition of heat to insure completion of the reaction.

(B) PREPARATION OF FATTY ACID-POLY- AMINE DERIVATIVE Example B-1 128 grams (1.25 moles) of diethylene triamine and 731 grams of tallow (2.5 acid equivalents) were heated together for 4 hours in the temperature range of 138 to 174 C. after which 26 grams of vacuum distillate were removed by vacuum stripping at 1 ml. The contents of the fiask solidified at room temperature to a waxy solid consisting principally of the tallow acid di-amide of diethylene triamine. A small proportion of glycerol liberated from the fat used as a source of fatty acid remained with the product. The overall nitrogen content was 5.91% and the HCl equivalent was 704.

Example B-Z 256 grams of diethylene triamine and 1,462 grams of tallow were heated at to 175 C. for 3 hours and 40 minutes. During the heating which was conducted under a vacuum, distillate was removed and collected. The residue in the flask comprised principally the tallow acid di-arnide of diethylene triamine and had a nitrogen content of 5.97% and an HCl equivalent of 712.

Example B-3 Example B-4 206 grams of diethylene triamine and 1,646 grams of a commercial tall oil fatty acid (sold as the trademarked product Acintol FA No. 1) were heated together at 150 to C. for three hours. The heating was conducted under vacuum and distillate was collected and removed. The residue in the flask comprised the tallow fatty acid amide of diethylene triamine.

(C) REACTION OF THE POLYOL DERIVATIVES OF (A) WITH THE FATTY ACID DERIVATIVES OF (B) Example C-1 200 grams of the product of Example B-1 and 56 grams of the product of Example A-1 were heated together for 2 hours in the temperature range of 77 to 125 C. The resulting condensate was a soft, water-soluble wax with marked surface active properties. The compound and its preparation are described more fully as Example III-2 of the parent case.

Example C-2 300 grams of the product of Example B-2 and 69 grams of the product of Example A-2 were heated together for 2% hours in the temperature range of 68 C. to 132 C. The resulting condensate was a soft, water dispersible wax with marked surface-active properties. It was also found to be a suitable anti-static additive. The preparation of this product is described in more detail as Example IIl-9 of the parent case.

Example C-3 233 grams of the product of Example B3 and 92 grams of the product of Example A-3 were heated together for two hours in the temperature range of 99 C. to 117 C. T he resulting condensate was a soft, water-dispersible 9 wax with marked surface-active properties. It was found suitable as an anti-static additive. The preparation of this compound is described in more detail as Example III- of the parent case.

Example C-4 733 grams of the product of Example B-4 and 220 grams of the product of Example A-l were heated together for two hours at a temperature of about 120 C. The product was found to be a' suitable anti-static additive.

Additives within the scope of the invention, the preparation of which was described above (i.e. C-1, C-2, C-3, C-4) and the preparations of Examples III-1, III-3 to lII-8 incl., and III-l1 to III-17 incl. of the parent case were incorporated in fuel formulations which exemplified the invention. Formulations may also be prepared containing conventional additives such as corrosion inhibitors, anti-knock materials and the like as well as mixtures of t-heinstant additives prepared as follows:

FORMULATIONS 1-18 To successive portions of JP-4 jet fuel add .02 weight percent of each of the products of Examples C-l to C-4 of the instant case and Examples III-1, III-3 to III-8 incl., III-11 to III-17 incl. of the parentcase. Each of these fuel formulations (i.e. JP-4 jet fuel plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 19-36 To successive portions of JP-4 jet fuel add .01 weight percent of each of the products of Examples C-l to C-4 of the instant case and Examples III-1, III-3 to III-8 incl., III-l1 to III-17 incl. of the parent case. Each of these fuel formulations (i.e. JP-4 fuel plus one specific additive) ha a resistivity of less than about 1X10 ohm centimeters and embodies the instant invention.

FORMULATIONS 37-54 To successive portions of JP-4 jet fuel add .005 weight percent of each of the products of Examples C1 to C-4 of the instant case and Examples III-1, III-3 to III-8 incl., III-11 to III-17 incl. of the parent case. Each of these fuel formulations (i.e. IP-4 fuel plus one specific additive) has a resistivity of less than about 1X10 ohm'centimeters and embodies the instant invention.

FORMULATIONS 55-72 To successive portions of kerosene add 1.8 weight percent of each of the products of Examples C-1 to C4 of the instant case and Examples III-1, III-3 to III-8 incl., III-11 to III-17 incl. of the parent case. Each of these fuel formulations (i.e. kerosene plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 73-90 To successive portions of non-leaded automotive gasoline add 0.5 weight percent of each of the products of Examples C-l to C-4 of the instant case and Examples Ill-1, III-3 to III-8 incl., III-11 to IlIl7 incl. of the parent case. Each of these fuel formulations (i.e. nonleaded automotive gasoline plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 91-108 To successive portions of aviation gasoline add 1.0 weight percent of each of the products of Examples C-l to C-4 of the instant case and Examples III-1, III-3 to I'II-8 incl., III-11 to III-17 incl. of the parent case. Each of these fuel formulations (i.e. aviation gasoline plus one specific additive) has a resistivity of less than about 1 10 ohm-centimeters and embodies the instant invention.

FORMULATIONS 109-126 ohm-centimeters and embodies the instant invention.

Formulations of the above type were tested to determine the effect of the additives on the resistivity of JP-4 jet fuel. The results of some of these tests are tabulated below:

Resistivit (ohm-cm.

Weight percent additive Additive 4. 0X10 2. 2X10" 7. 7X10 3. 4X10 1. 9X10 9. 0x10 4. 1x10 1. 9X10 1. 9X10 6. 9X10 3. 0X10 1. 2X10 3. 8x10 2. 0X10" 8. 6X10 4. 5X10 1. 1X10 8. 2X10 1. 3X10 3. 0X10 3. 2X10 1. 7X10 7. 7X10 4. 3X10 2.3)(10 N one.

Product of Example C-l cinch-Ono Or an Product of Example (3-2 Product of Example O-3 Product of Example C-4 Reaction product of A-1 and amino ethyl heptadecyl imidazoline Reaction product of A-1 and tallow diamide of diethylene triamine KID- O The above formulations were also tested for ability to build up a charge of static electricity. When the treated fuels were continuously pumped through a closed loop, no static build up was detected.

The term consisting essentially of, as used in the claims, includes compositions containing the named ingredients in the proportions stated and any other ingredients which do not deleteriously affect the compositions for the purposes stated in the specification.

Having described my invention, what is claimed is:

l. A hydrocarbon fuel having a resistivity of less than about 1 10 ohm-centimeters consisting essentially of a liquid hydrocarbon which forms an equilibrium explo sive mixture with air between about 20 F. and about F. and has a Reid vapor pressure of from about 0.1 to about 15 lbs/sq. inch and, as an anti-static additive, from 0.005 to 2.0 weight percent of a compound prepared by reacting a reactant (1) represented by the formula:

wherein:

R is a hydroxyl-free radical of a polyhydric alcohol, X is a halogen atom having an atomic weight greater than 30, x is a number from 3 to 6, and n is a number from 1 to x with a second reactant (2) a basic amino nitrogencontaining compound, which is a fatty acylation product of a polyalkylene polyamine which polyamine has from 3 to 5 amino groups; said reactants having been selected in such proportions that from one to three basic nitrogen atoms are supplied by reactant (2) for each halogen atom in reactant (1).

2. The fuel of claim 1 in which reactant (2) is a fatty acid amide.

3. The fuel of claim 1 in which reactant (2) is a cyclic nitrogen compound selected from the group consisting of imidazolines and tetrahydropyrimidines.

'4. The fuel of claim 1 in which the anti-static additive is a free base formed by contacting the reaction product acetic acid, lactic acid, tartaric acid, formic acid, stearic acid, benzene sulfonic acid, toluene sulfonic acid, hydrochloric acid and citric acid.

6. The fuel of claim 1 in which X is chlorine and x is 6.

7. The fuel of claim 6 in which reactant (1) is a sorbitol-epichlorohydrin condensate and reactant 2) is a tallow amide of diethylene triamine.

' 8, The fuel of claim 7 in which reactant (2)is a tallow di'amide of diethylene tria mine i 9. The fuel of claim 1 inwhich the liquid hydrocarbon is a low vapor pressure, wide-cut, gasoline type hydrocarbon of the nature of JP-4 jet fuel and having a Reid vapor pressure of from 2 to 3 pounds per square inch,

and the antistatic additive is present in amounts from 0.005 to 1.0 weight percent. I

10. The fuel of claim 9 in which reactant (1) is a sorvbitol-epichlorohydrin condensate and reactant (2) is a tallow diamide of diethylene triamine.

No references cited. 

1. A HYDROCARBON FUEL HAVING A RESISTIVITY OF LESS THAN ABOUT 1X1011 OHM-CENTIMETERS CONSISTING ESSENTIALLY OF A LIQUID HYDROCARBON WHICH FORMS AN EQUILIBRIUM EXPLOSIVE MIXTURE WITH AIR BETWEEN ABOUT -20*F. AND ABOUT 100*F. AND HAS A REIS VAPOR PRESSURE OF FROM ABOUT 0.1 TO MABOUT 15 LBS./SQ. INCH AND, AS AN ANTI-STATIC ADDITIVE, FROM 0.005 TO 2.0 WEIGHT PERCENT OF A COMPOUND PREPARED BY REACTING A REACTANT (1) REPRESENTED BY THE FORMULA: 